1973 Volume 46 Issue 1 Pages 178-183
The kinetics of racemization reactions of ethylenediaminetetraacetatocobaltate(III), CoIIIedta−, and trimethylenediaminetetraacetatocobaltate(III), CoIIItrdta−, were investigated in acid solutions. The rate law for the racemization of (+)546CoIIIedta− is:
where Ka is the equilibrium constant of the reaction:
The values of kr1 and kr2 at 120°C and at an ionic strength of 0.53 are 2.0×10−5 sec−1 and 5.6×10−4 sec−1 respectively. The rate law for the racemization of (+)589CoIIItrdta− is:
The value of k′r2 at 120°C and at an ionic strength of 0.53 is 1.9×10−5 l mol−1 sec−1. It is known that the rate of the racemization reaction of optically-active CoIIedta2− is accelerated by the presence of CoIIedta2− because of the electron-exchange reaction between these two species. In this paper, the electron-exchange reaction between CoIIItrdta− and CoIItrdta2− is also investigated by the utilization of the optical activity. This reaction proceeds faster than the reaction between CoIIIedta− and CoIIedta2−.
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